US4258121A - Photopolymerizable compositions - Google Patents

Photopolymerizable compositions Download PDF

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US4258121A
US4258121A US06/127,627 US12762780A US4258121A US 4258121 A US4258121 A US 4258121A US 12762780 A US12762780 A US 12762780A US 4258121 A US4258121 A US 4258121A
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group
substituted
photopolymerizable composition
photosensitive material
monomer
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Teruo Kojima
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing
    • Y10S430/109—Polyester
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing
    • Y10S430/111—Polymer of unsaturated acid or ester
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/12—Nitrogen compound containing
    • Y10S430/121—Nitrogen in heterocyclic ring

Definitions

  • This invention relates to photopolymerizable compositions and, more particularly, to a photopolymerizable composition comprising an unsaturated monomer, a photopolymerization initiator, and, if necessary, a linear organic high molecular weight polymer and a sensitizer.
  • the invention relates to photopolymerizable compositions useful for photosensitive layers of photosensitive printing plates, photoresists, etc.
  • a method of making image reproductions by photographic means using a photosensitive composition composed of a mixture of a polymerizable ethylenically unsaturated compound, a photopolymerization initiator, and, if necessary, a soluble polymer having film-forming ability, a thermal polymerization preventing agent, etc., is presently widely known.
  • 2,927,022, and 2,902,356 disclose that a photosensitive composition of this type has the ability to be hardened and insolubilized by irradiation with light and hence hardened images of the photopolymerizable composition can be formed by providing a film or layer of the photopolymerizable composition, exposing the film or layer through a negative of the desired image to light, and then removing unexposed portions with a suitable solvent.
  • the photopolymerizable composition of this type is very useful for making printing plates or resists.
  • photopolymerization initiators such as benzil, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone, etc., have been added to the compound to increase sensitivity.
  • photopolymerization initiators using these photopolymerization initiators, a long exposure time is required for hardening due to the low response of the photopolymerizable compositions.
  • one object of this invention is to provide high-sensitive photopolymerizable compositions.
  • Another object of this invention is to provide photopolymerizable compositions containing a polymerizable ethylenically unsaturated compound together with a photopolymerization initiator for increasing the photopolymerization speed of the photopolymerizable compositions.
  • the invention relates to a photopolymerizable composition containing a polymerizable ethylenically unsaturated compound and a photopolymerization initiator represented by general formula (I): ##STR2## wherein A represents an arylene group, a substituted arylene group, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkenylene group and R represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group; together with, if necessary, a linear organic high molecular weight polymer and further, if necessary, a sensitizer.
  • A represents an arylene group, a substituted arylene group, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkenylene group
  • R represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group
  • the polymerizable ethylenically unsaturated compound used in this invention contains at least two polymerizable ethylenically unsaturated groups per molecule.
  • Practical examples are esters of acrylic acid or methacrylic acid and polyols, bisacrylamides and vinylurethane compounds having two or more polymerizable vinyl groups per molecule.
  • Typical acrylic and methacrylic acid esters are esters of polyols having at least two aliphatic hydroxy groups, preferably having 2 to 5 aliphatic hydroxy groups and having from 2 to 12 carbon atoms.
  • diols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,4-butane diol, 1,5-pentane diol, polycyclohexane oxide, polystyrene oxide, cyclohexane diol, xylylene diol, di-( ⁇ -hydroxyethoxy)benzene; polyols such as glycerine, diglycerine, trimethylolpropane, triethylolpropane, pentaerythritol, and the like.
  • Suitable acrylates or methacrylates of polyols are compounds such as diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, etc., and are described in detail in U.S. Pat. Nos. 2,760,863, 2,791,504, 3,060,023 and 3,870,524.
  • the bisacrylamide can be alkylene or arylene but the alkylene bisacrylamide is preferred.
  • alkylene bisacrylamide examples are methylene-bis-acrylamide, ethylene-bis-acrylamide, propylene-bis-acrylamide, butylene-bis-acrylamide, pentamethylene-bis-acrylamide, hexamethylene-bis-acrylamide, heptamethylene-bis-acrylamide, octamethylene-bis-acrylamide, N,N',N"-tris-acrylamide from diethylene triamine, xylene bisacrylamide, etc., as described in U.S. Pat. Nos. 2,927,022 and 3,486,903 and British Pat. No.
  • the corresponding methacrylamides and acrylamides and methacrylamides derived from polyamides and other diamines, said amines may have 2 to 18 carbon atoms, be branched and contain --O-- or --NH-- or --NR (R lower alkyl) groups in the molecule chain or aliphatic or aromatic rings.
  • the vinyl urethane compounds can be prepared by reacting a polyisocyanate compound having two or more isocyanate groups per molecule with a vinyl monomer containing a hydroxy group shown by general formula (II):
  • the polyisocyanate used in making the vinylurethane compounds may have two or more isocyanate groups in the molecule and preferably has about 6 to 20 carbon atoms.
  • Examples of the polyisocyanate are hexamethylenediisocyanate, octamethylenediisocyanate, xylylenediisocyanate, tolylene-2,4-diisocyanate, 1,5-naphthalenediisocyanate, 4,4'-diphenylmethanediisocyanate and triphenylmethanetriisocyanate.
  • the compounds having two or more polymerizable ethylenically unsaturated groups per molecule and useful as the ethylenically unsaturated compound are polyester polyacrylates, polyester polymethacrylates, epoxy acrylates, epoxy methacrylates, etc., described in Japanese Pat. Application (OPI) Nos. 32003/73 (the term "OPI” as used herein refers to a "published unexamined Japanese patent application") and 30504/73 and U.S. Pat. No. 3,732,107.
  • the photopolymerization initiators which are characteristic of the photopolymerizable compositions of this invention can be prepared by the method described in, for example, L. Bauer, et al., Journal of Organic Chemistry, 24, 1293 (1959) under basic conditions using the compound represented by general formula (III): ##STR3## wherein A is defined as in formula (I); prepared according to the method described in G. F. Jauber, Berichte der Deutschen Chemischentechnik, Vol. 28, pages 360-364 (1895); the method described in D. E. Ames, et al., Journal of Chemistry Society, 3518-3521 (1955); or the method described in M. A. Stolberg, et al., Journal of the American Chemical Society, 79, 2615-2617 (1957); and an organic sulfonic acid chloride represented by the formula:
  • the reaction of the compound of formula (III) with the sulfonic acid chloride proceeds under basic conditions using water or an organic solvent as a solvent.
  • organic solvents organic solvents other than alcohols and phenols are preferred (for example, acetone, methyl ethyl ketone, tetrahydrofuran, 1,4-dioxane).
  • Amines such as diethylamine, triethylamine, pyridine, etc., are preferred as the base.
  • a water-soluble inorganic base for example, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide
  • a reaction temperature of about 0° to 50° C. is preferred for both water and the organic solvent.
  • the compound of formula (III) and the sulfonic acid chloride react in about equal moles and the base is preferably used in an equivalent to three times equivalent amount based on the compound of formula (III).
  • the arylene group A in formula (I) is preferably a monocyclic or bicyclic arylene group such as a phenylene group, a naphthylene group, etc., more practically an o-phenylene group, a 1,8-naphthylene group, a 2,3-naphthylene group, etc.
  • the substituted arylene group is one described above having a substituent such as a halogen atom (e.g., a chlorine, bromine, etc.), a nitro group, an acetylamino group, etc., and is practically a bromophenylene group, a chlorophenylene group, a nitrophenylene group, an acetylaminophenylene group, a bromonaphthylene group, a chloronaphthylene group, a nitronaphthylene group, etc.
  • a halogen atom e.g., a chlorine, bromine, etc.
  • a halogen atom e.g., a chlorine, bromine, etc.
  • a halogen atom e.g., a chlorine, bromine, etc.
  • a halogen atom e.g., a chlorine, bromine, etc.
  • a halogen atom e.g.,
  • the alkylene group A is a straight chain, branched chain, or cyclic alkylene group having preferably 1 to about 6 carbon atoms such as, for example, a methylene group, an ethylene group, a propylene group, a cyclobutylene group, a cyclohexylene group, etc.
  • the alkylene group can bear one or more substituents such as, for example, a phenyl group, a naphthyl group or an alkyl group, preferably a straight chain alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group and an n-butyl group.
  • Practical examples of substituted alkylene groups are a phenylethylene group, a diphenylethylene group, etc.
  • the alkenylene group A preferably has 2 to 4 carbon atoms, may be a straight chain, branched chain, or cyclic alkenylene and preferably is a straight chain alkenylene, and is practically a vinylidene group, a butenylene group, etc.
  • the alkenylene group may be substituted by an aryl group such as a phenyl group or a lower alkyl group preferably an alkyl group having 1 to 2 carbon atoms (e.g., a methyl group or an ethyl group) and is practically a phenylvinylidene group, a diphenylvinylidene group, etc.
  • the alkyl group R in formula (I) is a straight chain, branched chain or cyclic alkyl group (preferably a straight chain alkyl group) preferably having 1 to 18 carbon atoms.
  • a straight chain alkyl group preferably a straight chain alkyl group
  • the substituted alkyl group R is one described above having a halogen atom such as a chlorine, bromine, or fluorine atom, etc., or an alkoxy group having 1 to 4 and preferably 1 or 2 carbon atoms such as a methoxy group, etc., as the substituent.
  • a halogen atom such as a chlorine, bromine, or fluorine atom, etc.
  • an alkoxy group having 1 to 4 and preferably 1 or 2 carbon atoms such as a methoxy group, etc.
  • Practical examples are a 2-chloroethyl group, a 2-methoxyethyl group, etc.
  • the aryl group R is preferably a monocyclic or bicyclic aryl group having 6 to 12 carbon atoms such as, for example, a phenyl group, a naphthyl group, etc.
  • the aryl group may be substituted by an alkyl group having 1 or 2 carbon atoms such as a methyl group or an ethyl group; an alkoxy group having 1 or 2 carbon atoms such as a methoxy group or an ethoxy group, or a halogen atom such as a chlorine atom, etc.
  • Practical examples are a methylphenyl group, a dimethylphenyl group, a methoxyphenyl group, a chlorophenyl group, a methoxynaphthyl group, etc.
  • the compounds having the structures shown in Table 1 are particularly useful as the photopolymerization initiators used in this invention.
  • N-hydroxy-1,8-naphthalimide thus prepared and while stirring the mixture at room temperature, 1.0 g of ethanesulfonyl chloride was added dropwise to the mixture over a 5 minute period. After further stirring the resultant mixture for 1 hour at room temperature, precipitates formed were collected and recrystallized from a mixture of benzene and ethanol to provide 1.4 g of N-hydroxy-1,8-naphthalimidoethanesulfinic acid ester (melting point 159°-162° C.).
  • the amount of the photopolymerization initiator used in this invention is usually very small and the use of an excessive amount causes undesirable results such as blocking effective radiation, etc.
  • the amount of the photopolymerization initiator of formula (I) used in this invention is usually about 0.1 to 20% by weight, preferably about 1 to 10% by weight based on the amount of the ethylenically unsaturated compound.
  • the linear organic high molecular weight polymer used in this invention are found in many conventional photopolymerizable compositions and must be compatible with the polymerizable ethylenically unsaturated compound. Typical examples are the binders disclosed in U.S. Pat. Nos. 3,458,311, 3,804,631, 3,930,865 and 4,147,549.
  • the molecular weight for these polymers varies depending on the kind of the polymer, but is generally about 5,000 to 2,000,000 and preferably about 10,000 to 1,000,000. Any linear organic high molecular weight polymer that is compatible with the ethylenically unsaturated monomer can be used in the present invention, and water-soluble or weak aqueous alkali-solution soluble polymers are preferred.
  • the linear organic high molecular weight polymer is used not only as the film-forming agent of the photopolymerizable composition of this invention but is also selected to enable the use of a water developer, a weak aqueous alkali developer, or an organic solvent developer.
  • a water-soluble linear high molecular weight polymer such as a polymer having a carboxylic acid group or a sulfonic acid group in a side chain thereof (e.g., polymers in which methacrylic acid, acrylic acid, itaconic acid or 2-acrylamido-2-methylpropane sulfonic acid is a comonomer) is used, water development is applicable.
  • water soluble high molecular weight polymers there are addition polymers having carboxylic acid groups in the side chain thereof, such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, partially esterificated maleic acid copolymers, etc., and acid cellulose derivatives having carboxylic acid groups in the side chains thereof.
  • Polymers prepared by reacting a cyclic acid anhydride with addition polymerized polymers containing hydroxy groups can also be useful as the linear organic polymers (for example, reaction products of an aliphatic cyclic acid anhydride such as succinic anhydride, glutaric anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, an aromatic cyclic acid anhydride such as phthalic anhydride, trimellitic acid anhydride, 1,8-naphthalic anhydride and an addition polymer containing hydroxy groups such as homopolymers or copolymers of 2-hydroxyethylmethacrylate, 2-hydroxyethylacrylate, 2-hydroxypropylmethacrylate, 2-hydroxypropylacrylate, N-methylolacrylamide, p-hydroxymethacrylanilide, N-(5-hydroxy- ⁇ -naphthyl)methacrylamide).
  • an aliphatic cyclic acid anhydride such as succinic
  • water-soluble linear organic high molecular weight polymers used in this invention are polyvinyl pyrrolidone, polyethylene oxide, etc.
  • alcohol-soluble nylons and the polyethers of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin are useful for increasing the strength of the hardened films or layers in this invention.
  • linear organic high molecular weight polymers may be incorporated in the photopolymerizable composition in almost any desired amount but if the amount is over about 90% by weight of the composition, the results obtained are undesirable from the standpoint of the image strength, etc.
  • a sensitizer which can increase the photopolymerization speed of the photopolymerizable composition can be used together with the photopolymerization initiator shown by formula (I).
  • sensitizers are carbonyl compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, thioxanthone, p-(dimethylamino)phenylstyryl ketone, benzil, dibenzalacetone, p-(dimethylamino)phenyl-p-methylstyryl ketone, benzophenone, p-(d
  • sensitizers used in this invention are the compounds of the formula (IV) described in U.S. Pat. No. 3,870,524: ##STR27## wherein R 3 represents an alkyl group and preferably a straight chain alkyl group having 1 to 4 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.) or a substituted alkyl group (e.g., a 2-hydroxyethyl group, a 2-methoxyethyl group, a carboxymethyl group, a 2-carboxyethyl group, etc.), R 4 represents an alkyl group, preferably a straight chain alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, etc.) or a substituted or unsubstituted, mono- or bicyclic aryl group having 6 to 12 carbon atoms (e.g., a pheny
  • the aryl group R 4 may be substituted with, for example, an alkyl group having 1 to 2 carbon atoms (e.g., a methyl group, an ethyl group), an alkoxy group having 1 to 2 carbon atoms (e.g., a methoxy group, an ethoxy group), a halogen atom (e.g., a chlorine atom, a bromine atom), a hydroxy group, a carboxy group.
  • the alkyl group R 3 may be substituted by, e.g., a hydroxy group, an alkoxy group (preferably an alkoxy group having 1 to 2 carbon atoms), and a carboxy group.
  • the amount of the sensitizer used in the invention is usually very small and the use of an excessive amount causes undesirable results such as shielding of actinic light, etc.
  • the amount of the sensitizer used in this invention is usually about 0.01 to 20% by weight, preferably about 1 to 10% by weight based on the amount of the ethylenically unsaturated compound used.
  • a thermal polymerization inhibitor to the photopolymerizable composition in an amount of about 0.005 to 5% by weight of the amount of the ethylenically unsaturated compound to prevent the occurrence of the unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or preservation of the photopolymerizable composition of this invention.
  • thermal polymerization inhibitors examples include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl-catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, N-nitrosophenylhydroxylamine primary selium salt, etc.
  • Suitable support materials can be chosen from among a variety of meterials which do not directly chemically react with the coating composition.
  • Such support materials include fiber base materials such as paper, polyethylene-coated paper, polypropylene-coated paper, parchment, cloth, etc.; sheets and foils of such metals as aluminum particularly grained aluminum, anodized aluminum or grained and anodized aluminum, copper, magnesium, zinc, etc.; glass and glass coated with such metals as chromium, chromium alloys, steel, silver, gold, platinum, etc.; synthetic resin and polymeric materials such as poly(alkyl acrylates), e.g., poly(methyl methacrylate), polyester film base--e.g., poly(ethylene terephthalate), poly(vinyl acetals), polyamides--e.g., nylon and cellulose ester film base--e.g., cellulose acetate, cellulose nitrate, cellulose ester with a hydrolyzed surface, cellulose acetate
  • Light sources which may be used in exposing the photopolymerizable composition of the present invention include broad spectrum light sources, filtered or unfiltered, including xenon or carbon arcs, narrow spectrum sources such as mercury lamps which emit within low (UV) to medium (visible light) wavelengths, and laser sources.
  • dyes or pigments may be added to the composition for coloring and further inorganic fillers may be added for improving the properties of the hardened films or layers of the compositions.
  • An aluminum sheet which was grained by a nylon brush and treated with silicate was coated with the following photosensitive coating composition using a rotary coating machine and dried for 3 minutes at 100° C. to form a photosensitive layer, thereby a photosensitive plate was prepared.
  • the photosensitive plate was exposed through a step wedge (density step difference of 0.15 and density step number of 0-15 steps) to a light source (a metal halide lamp of 0.5 kw) at a distance of 50 cm from the light source for 10 minutes using a vacuum printing frame and thereafter developed using a developer having the following composition.
  • a step wedge density step difference of 0.15 and density step number of 0-15 steps
  • a light source a metal halide lamp of 0.5 kw
  • the maximum step numbers on the step wedge corresponding to the reproduced images are shown in Table 2 as the sensitivity. A higher step number indicates a higher sensitivity. Also, the sensitivity in case of adding no photopolymerization initiator of formula (I) is shown in Table 2 as Comparison Example 1.
  • Each of the photosensitive plates was exposed through a step wedge for 3 minutes using a Plano PS printer A3 (made by Fuji Photo Film Co., Ltd.) and then developed using the developer having the same composition as in Examples 1 to 4.
  • the maximum step number of the step wedge corresponding to the reproduced image is shown in Table 3 as the sensitivity of each sample. Also, the sensitivity using Michler's ketone alone is shown in Table 3 as Comparison Example 2.
  • Each of the photosensitive plates was exposed through a step wedge for 3 minutes using Plano PS Printer A3 (made by Fuji Photo Film Co.) and then developed using the developer having the same composition as in Examples 1 to 4.
  • the compounds of formula (IV) used in these examples are shown in Table 4.
  • the sensitivity of each sample is shown in Table 5 as the maximum step number of the step wedge.
  • the sensitivity in case of using the compounds of formula (IV) solely are shown in Table 5 as Comparison Examples 3 to 8.

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US06/127,627 1979-03-06 1980-03-06 Photopolymerizable compositions Expired - Lifetime US4258121A (en)

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JP54-25750 1979-03-06
JP2575079A JPS55118030A (en) 1979-03-06 1979-03-06 Photopolymerizable composition

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE31103E (en) * 1977-01-14 1982-12-14 Raychem Corporation Crosslinking agent for polymers and wire construction utilizing crosslinked polymers
US4371605A (en) * 1980-12-09 1983-02-01 E. I. Du Pont De Nemours And Company Photopolymerizable compositions containing N-hydroxyamide and N-hydroxyimide sulfonates
US4425424A (en) 1982-04-08 1984-01-10 Eastman Kodak Company Dye-forming compositions
WO1984000888A1 (en) * 1982-09-01 1984-03-15 Univ Southern California Substituted n-benzenesulfonyloxyphthalimides
US4439517A (en) * 1982-01-21 1984-03-27 Ciba-Geigy Corporation Process for the formation of images with epoxide resin
US4454218A (en) * 1982-09-13 1984-06-12 E. I. Du Pont De Nemours And Company N-Alkylindolylidene and N-alkylbenzo-thiazolylidene alkanones as sensitizers for photopolymer compositions
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US5272042A (en) * 1989-03-14 1993-12-21 International Business Machines Corporation Positive photoresist system for near-UV to visible imaging
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US5585218A (en) * 1993-06-02 1996-12-17 Sumitomo Chemical Company, Limited Photoresist composition containing alkyletherified polyvinylphenol
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US4371605A (en) * 1980-12-09 1983-02-01 E. I. Du Pont De Nemours And Company Photopolymerizable compositions containing N-hydroxyamide and N-hydroxyimide sulfonates
US4532332A (en) * 1981-08-17 1985-07-30 Ciba-Geigy Corporation N-(hydroxypolyoxaalkylene)phthalimides and succinimides and acrylate esters thereof
US4439517A (en) * 1982-01-21 1984-03-27 Ciba-Geigy Corporation Process for the formation of images with epoxide resin
US4425424A (en) 1982-04-08 1984-01-10 Eastman Kodak Company Dye-forming compositions
WO1984000888A1 (en) * 1982-09-01 1984-03-15 Univ Southern California Substituted n-benzenesulfonyloxyphthalimides
US4454218A (en) * 1982-09-13 1984-06-12 E. I. Du Pont De Nemours And Company N-Alkylindolylidene and N-alkylbenzo-thiazolylidene alkanones as sensitizers for photopolymer compositions
US4618564A (en) * 1984-05-25 1986-10-21 Ciba-Geigy Corporation Process for production of positive images using sulfonic acid precursors
EP0166682A2 (de) * 1984-05-25 1986-01-02 Ciba-Geigy Ag Verfahren zur positiven Bilderzeugung
EP0166682A3 (en) * 1984-05-25 1987-03-04 Ciba-Geigy Ag Process for obtaining positive images
US4737426A (en) * 1985-05-15 1988-04-12 Ciba-Geigy Corporation Cyclic acetals or ketals of beta-keto esters or amides
US4957988A (en) * 1985-05-22 1990-09-18 Ciba-Geigy Corporation Process and polymers for the production of images
US4770976A (en) * 1986-03-20 1988-09-13 Basf Aktiengesellschaft Phenanthroimidazole compounds, their preparation, photopolymerizable coating and recording materials, and lithographic layers produced using these
US5272042A (en) * 1989-03-14 1993-12-21 International Business Machines Corporation Positive photoresist system for near-UV to visible imaging
US5585218A (en) * 1993-06-02 1996-12-17 Sumitomo Chemical Company, Limited Photoresist composition containing alkyletherified polyvinylphenol
EP0709410A2 (de) 1994-10-26 1996-05-01 OCG Microelectronic Materials, Inc. Polymere
US5593812A (en) * 1995-02-17 1997-01-14 International Business Machines Corporation Photoresist having increased sensitivity and use thereof
US5770345A (en) * 1995-02-17 1998-06-23 International Business Machines Corporation Photoresist having increased sensitivity and use thereof
US5753412A (en) * 1995-02-17 1998-05-19 International Business Machines Corporation Photoresist having increased sensitivity and use thereof
US20030166750A1 (en) * 1995-12-04 2003-09-04 Koletar Gabor I. Method for the production of anhydride modified polyvinyl acetals useful for photosensitive compositions
US20040023159A1 (en) * 2002-03-29 2004-02-05 Katsuya Sakayori Photoradical polymerization initiator, radical generator, photosensitive compound and photosensitive resin composition containing these materials and product or its accessory portions using the composition
US7410746B2 (en) * 2002-03-29 2008-08-12 Dai Nippon Printing Co., Ltd. Photoradical polymerization initiator, radical generator, photosensitive compound and photosensitive resin composition containing these materials and product or its accessory portions using the composition
US8715901B2 (en) * 2004-05-26 2014-05-06 Jsr Corporation Resin composition for forming fine pattern and method for forming fine pattern
US20070259287A1 (en) * 2004-05-26 2007-11-08 Hirokazu Sakakibara Resin Composition for Forming Fine Pattern and Method for Forming Fine Pattern
US20090233229A1 (en) * 2008-03-11 2009-09-17 Shota Suzuki Lithographic printing plate precursor and method of lithographic printing
EP2100731A3 (de) * 2008-03-11 2010-09-29 FUJIFILM Corporation Lithographiedruckplattenvorläufer und Lithographiedruckverfahren
US8142983B2 (en) 2008-03-11 2012-03-27 Fujifilm Corporation Lithographic printing plate precursor and method of lithographic printing
US20100028807A1 (en) * 2008-07-30 2010-02-04 Sumitomo Chemical Company, Ltd. Imide Compound and Chemically Amplified Resist Composition Containing The Same
KR20100013264A (ko) * 2008-07-30 2010-02-09 스미또모 가가꾸 가부시키가이샤 이미드 화합물 및 이를 포함하는 화학적으로 증폭된 레지스트 조성물
US8329377B2 (en) * 2008-07-30 2012-12-11 Sumitomo Chemical Company, Limited Imide compound and chemically amplified resist composition containing the same
CN101638388A (zh) * 2008-07-30 2010-02-03 住友化学株式会社 二酰亚胺类化合物及包含该化合物的化学增幅抗蚀剂组合物
US11325368B2 (en) 2017-03-27 2022-05-10 Flint Group Germany Gmbh Method for producing pictorial relief structures

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GB2045264A (en) 1980-10-29
JPS626223B2 (de) 1987-02-09
GB2045264B (en) 1982-12-01
DE3008657A1 (de) 1980-09-11
JPS55118030A (en) 1980-09-10

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